CN105903467A - Preparation method of palladium-only automobile exhaust catalyst - Google Patents
Preparation method of palladium-only automobile exhaust catalyst Download PDFInfo
- Publication number
- CN105903467A CN105903467A CN201610268277.1A CN201610268277A CN105903467A CN 105903467 A CN105903467 A CN 105903467A CN 201610268277 A CN201610268277 A CN 201610268277A CN 105903467 A CN105903467 A CN 105903467A
- Authority
- CN
- China
- Prior art keywords
- carrier
- preparation
- exhaust catalyst
- ball milling
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Combustion & Propulsion (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to automobile exhaust catalysts, in particular to a preparation method of a palladium-only automobile exhaust catalyst. The preparation method includes subjecting zirconia, cerium oxide and lanthanum powder to mixed ball milling by mass, and then adding alumina powder for continuous ball milling to obtain compound powder; preparing the compound powder into slurry with deionized water, soaking a carrier into the slurry prior to drying and sintering, then soaking the sintered carrier into palladium chloride ammonia solution, and taking out the carrier for drying, sintering and cooling; soaking the carrier into potassium borohydride solution for reaction prior to washing with the deionized water; then soaking the carrier into solution prepared from the palladium chloride, ammonia water, EDTA (ethylene diamine tetraacetic acid), hydrazine hydrate and deionized water for reaction prior to taking out for washing and drying. Catalyst powder particles are refined by ball milling, and the grain size reaches nanoscale; meanwhile, activity of the catalyst is improved by lanthanum; palladium is further plated on the carrier, and the plating is uniform, compact, good in chemical stability, high in hardness, good in lubricity and high in wear resistance and anti-scuffing property.
Description
Technical field
The present invention relates to auto-exhaust catalyst, specifically the preparation method of Pd-only automobile exhaust catalyst.
Background technology
Along with the increase of automobile pollution, CO, HC, NO that automobile discharges in airXMore and more.At present, many countries have taken strict control emission measure to motor vehicle exhaust emission.Therefore the process of vehicle exhaust is increasingly becoming important problem.In the prior art, be to realize by installing catalytic cleaner additional the control of motor vehicle exhaust emission, and catalytic cleaner it is crucial that catalyst.Catalyst generally uses three-decker to be i.e. made up of active component, washcoat and carrier.From RE perovskite oxide (PTO) since tail gas catalyzed, having produced Lacking oxygen owing to its A, B position can replace, such catalyst has bigger price advantage to noble metal catalyst simultaneously so that such catalyst becomes the focus of research.But, the PTO catalytic performance of existing one-component is the best, poor stability, it is impossible to meets increasingly serious motor vehicle exhaust emission and pollutes.
Summary of the invention
For above-mentioned technical problem, the present invention provides a kind of stable performance, the preparation method of lower-cost Pd-only automobile exhaust catalyst.
The technical solution used in the present invention is: the preparation method of Pd-only automobile exhaust catalyst, and it comprises the following steps:
(1) press mass fraction by zirconium oxide, cerium oxide and lanthanum powder mixing and ball milling, be subsequently adding alumina powder and continue ball milling, obtain composite powder；
(2) above-mentioned composite powder deionized water is configured to slurry, more pretreated cordierite carrier is immersed in slurry, then take out, and blow away slurry unnecessary in duct, then carry out drying, roasting；
(3) then carrier is immersed in Palladous chloride. ammonia solution, then take out dry, roasting, cooling；
(4) again carrier is immersed in solution of potassium borohydride and react, be then washed with deionized；
(5) then carrier is immersed reaction in the solution by the preparation of Palladous chloride., ammonia, EDTA, hydrazine hydrate and deionized water, then take out washing, be dried.
As preferably, in described composite powder, zirconium oxide accounts for 4 8wt%, and cerium oxide accounts for 15 20wt%, and lanthanum accounts for 2 4wt%, and surplus is aluminium oxide.
As preferably, the mixing and ball milling time is 30 50h, and continuing Ball-milling Time is 20 40h.
As preferably, ball milling uses the rotating speed of 180 220r/min, and ratio of grinding media to material is (9 10): 1.
As preferably, the immersion time in step (2) is 2min, uses 130 DEG C of dry 3h, 600 DEG C of roasting 1h.
As preferably, in step (3), the concentration of Palladous chloride. ammonia solution is 1g/L, and the immersion time is 3h, uses 120 DEG C of dry 4h, 500 DEG C of roasting 2h.
As preferably, the response time in step (4) is 20-30min.
As preferably, the response time in step (5) is 20-30min, is washed with deionized to neutrality after taking-up, then 100 DEG C of dry 4h.
As can be known from the above technical solutions, the present invention makes catalyst fines grain refine by ball milling, and its crystallite dimension reaches nanoscale；Meanwhile, use lanthanoid metal that the activity of catalyst is improved；The present invention also carries out plating palladium on carrier, and not only coating is uniform, fine and close, and chemical stability is good, and hardness is high, and lubricity is good, wear-resistant strong with anti-scuffing function.
Detailed description of the invention
The present invention is described more detail below, and illustrative examples and explanation in this present invention are used for explaining the present invention, but not as a limitation of the invention.
The preparation method of Pd-only automobile exhaust catalyst, it comprises the following steps:
First pressing mass fraction by zirconium oxide, cerium oxide and lanthanum powder mixing and ball milling 30 50h, add aluminium oxide and continue Ball-milling Time 20 40h, obtain composite powder, wherein zirconium oxide accounts for 4 8wt%, and cerium oxide accounts for 15 20wt%, and lanthanum accounts for 2 4wt%, and surplus is aluminium oxide；In mechanical milling process, use the rotating speed of 180 220r/min, (9 10): the ratio of grinding media to material of 1, so can obtain nano level composite powder.In mechanical milling process, owing to aluminium oxide ball milling can occur stress-induced isomer phase transformation, the α-Al of generation2O3Unfavorable to catalytic performance, so should participate in again grinding after ball milling zirconium oxide, cerium oxide and lanthanum powder；And lanthanum powder answers early stage and zirconium oxide, cerium oxide to be mixed together ball milling, otherwise it is difficult to refinement.The present invention first avoids aluminium oxide and only ball milling zirconium oxide, cerium oxide and lanthanum powder be to a certain extent, then add aluminium oxide and continue ball milling, zirconium oxide can be made to be solidly soluted into completely in cerium oxide, reduce the lattice paprmeter of cerium oxide, can make lanthanum highly dispersed in the solid solution of cerium oxide-cerium oxide simultaneously；Therefore, this ball-milling technology not only can obtain cerium oxide-cerium oxide solid solution, and has refined lanthanum powder, and whole composite powder particle diameter can reach 60 90nm.
Acquisition nanometer grade composit powder is last, it is configured to slurry with deionized water, again pretreated cordierite carrier is immersed in slurry, take out after about 1min, and blow away slurry unnecessary in duct, immersing 1min in slurry after drying again, then 130 DEG C of dry 3h, 600 DEG C of roasting 1h, so can obtain the impregnating slurry layer of even compact on carrier.
After slurry coats, carrier is immersed in the Palladous chloride. ammonia solution of 1g/L, magnetic agitation 4h, make to adsorb on carrier palladium ion, then take out, blow down redundant solution, dry, use 120 DEG C of dry 4h, 500 DEG C of roasting 2h, cooling；Carrier is immersed reaction 20-30min in solution of potassium borohydride again, makes the palladium ion of absorption on carrier be reduced to simple substance palladium, be then washed with deionized；Then the carrier after reduction is immersed and the solution by the preparation of Palladous chloride., ammonia, EDTA, hydrazine hydrate and deionized water reacts 20-30min, then take out and be washed with deionized to neutrality, finally dry, 100 DEG C of dry 4h, thus obtain the catalyst being coated with simple substance palladium.
Embodiment 1
By mass fraction, zirconium oxide, cerium oxide and lanthanum powder are mixed, use the rotating speed of 180r/min, the ratio of grinding media to material ball milling 30h of 9:1, adding aluminium oxide and continue Ball-milling Time 20h, obtain composite powder, wherein zirconium oxide accounts for 4wt%, cerium oxide accounts for 15wt%, and lanthanum accounts for 2wt%, and surplus is aluminium oxide；Then with deionized water, composite powder is configured to slurry, then pretreated cordierite carrier is immersed in slurry, take out after about 1min, and blow away slurry unnecessary in duct, after drying, immerse 1min in slurry, then 130 DEG C of dry 3h, 600 DEG C of roasting 1h again；After slurry coats, carrier is immersed in the Palladous chloride. ammonia solution of 1g/L, magnetic agitation 4h, then take out, blow down redundant solution, dry, use 120 DEG C of dry 4h, 500 DEG C of roasting 2h, cooling；Carrier is immersed reaction 20min in solution of potassium borohydride again, is then washed with deionized；Then carrier is immersed in the solution by the preparation of Palladous chloride., ammonia, EDTA, hydrazine hydrate and deionized water and react 20min, then take out and be washed with deionized to neutrality, finally dry, 100 DEG C of dry 4h, it is thus achieved that palladium load capacity is the catalyst of 1g/L；Testing this catalyst, it reaches 98.5% to the conversion ratio of CO, HC and NO, and initiation temperature is between 150 170 DEG C.
Embodiment 2
By mass fraction, zirconium oxide, cerium oxide and lanthanum powder are mixed, use the rotating speed of 200r/min, the ratio of grinding media to material ball milling 40h of 10:1, adding aluminium oxide and continue Ball-milling Time 30h, obtain composite powder, wherein zirconium oxide accounts for 6wt%, cerium oxide accounts for 18wt%, and lanthanum accounts for 3wt%, and surplus is aluminium oxide；Then with deionized water, composite powder is configured to slurry, then pretreated cordierite carrier is immersed in slurry, take out after about 1min, and blow away slurry unnecessary in duct, after drying, immerse 1min in slurry, then 130 DEG C of dry 3h, 600 DEG C of roasting 1h again；After slurry coats, carrier is immersed in the Palladous chloride. ammonia solution of 1g/L, magnetic agitation 4h, then take out, blow down redundant solution, dry, use 120 DEG C of dry 4h, 500 DEG C of roasting 2h, cooling；Carrier is immersed reaction 25min in solution of potassium borohydride again, is then washed with deionized；Then carrier is immersed in the solution by the preparation of Palladous chloride., ammonia, EDTA, hydrazine hydrate and deionized water and react 25min, then take out and be washed with deionized to neutrality, finally dry, 100 DEG C of dry 4h, it is thus achieved that palladium load capacity is the catalyst of 2g/L；Testing this catalyst, it reaches 99.2% to the conversion ratio of CO, HC and NO, and initiation temperature is between 130 150 DEG C.
Embodiment 3
By mass fraction, zirconium oxide, cerium oxide and lanthanum powder are mixed, use the rotating speed of 220r/min, the ratio of grinding media to material ball milling 50h of 10:1, adding aluminium oxide and continue Ball-milling Time 40h, obtain composite powder, wherein zirconium oxide accounts for 8wt%, cerium oxide accounts for 20wt%, and lanthanum accounts for 4wt%, and surplus is aluminium oxide；Then with deionized water, composite powder is configured to slurry, then pretreated cordierite carrier is immersed in slurry, take out after about 1min, and blow away slurry unnecessary in duct, after drying, immerse 1min in slurry, then 130 DEG C of dry 3h, 600 DEG C of roasting 1h again；After slurry coats, carrier is immersed in the Palladous chloride. ammonia solution of 1g/L, magnetic agitation 4h, then take out, blow down redundant solution, dry, use 120 DEG C of dry 4h, 500 DEG C of roasting 2h, cooling；Carrier is immersed reaction 30min in solution of potassium borohydride again, is then washed with deionized；Then carrier is immersed in the solution by the preparation of Palladous chloride., ammonia, EDTA, hydrazine hydrate and deionized water and react 30min, then take out and be washed with deionized to neutrality, finally dry, 100 DEG C of dry 4h, it is thus achieved that palladium load capacity is the catalyst of 2g/L；Testing this catalyst, it reaches 98.7% to the conversion ratio of CO, HC and NO, and initiation temperature is between 140 160 DEG C.
The technical scheme provided the embodiment of the present invention above is described in detail, principle and the embodiment of the embodiment of the present invention are set forth by specific case used herein, and the explanation of above example is only applicable to help to understand the principle of the embodiment of the present invention；Simultaneously for one of ordinary skill in the art, according to the embodiment of the present invention, all will change in detailed description of the invention and range of application, in sum, this specification content should not be construed as limitation of the present invention.
Claims (8)
1. the preparation method of Pd-only automobile exhaust catalyst, it comprises the following steps:
(1) press mass fraction by zirconium oxide, cerium oxide and lanthanum powder mixing and ball milling, be subsequently adding alumina powder and continue ball milling, obtain composite powder；
(2) above-mentioned composite powder deionized water is configured to slurry, more pretreated cordierite carrier is immersed in slurry, then take out, and blow away slurry unnecessary in duct, then carry out drying, roasting；
(3) then carrier is immersed in Palladous chloride. ammonia solution, then take out dry, roasting, cooling；
(4) again carrier is immersed in solution of potassium borohydride and react, be then washed with deionized；
(5) then carrier is immersed reaction in the solution by the preparation of Palladous chloride., ammonia, EDTA, hydrazine hydrate and deionized water, then take out washing, be dried.
The preparation method of auto-exhaust catalyst the most according to claim 1, it is characterised in that: in described composite powder, zirconium oxide accounts for 4 8wt%, and cerium oxide accounts for 15 20wt%, and lanthanum accounts for 2 4wt%, and surplus is aluminium oxide.
The preparation method of auto-exhaust catalyst the most according to claim 1, it is characterised in that: the mixing and ball milling time is 30 50h, and continuing Ball-milling Time is 20 40h.
The preparation method of auto-exhaust catalyst the most according to claim 1, it is characterised in that: ball milling uses the rotating speed of 180 220r/min, and ratio of grinding media to material is (9 10): 1.
The preparation method of auto-exhaust catalyst the most according to claim 1, it is characterised in that: the immersion time in step (2) is 2min, uses 130 DEG C of dry 3h, 600 DEG C of roasting 1h.
The preparation method of auto-exhaust catalyst the most according to claim 1, it is characterised in that: in step (3), the concentration of Palladous chloride. ammonia solution is 1g/L, and the immersion time is 3h, uses 120 DEG C of dry 4h, 500 DEG C of roasting 2h.
The preparation method of auto-exhaust catalyst the most according to claim 1, it is characterised in that: the response time in step (4) is 20-30min.
The preparation method of auto-exhaust catalyst the most according to claim 1, it is characterised in that: the response time in step (5) is 20-30min, is washed with deionized to neutrality after taking-up, then 100 DEG C of dry 4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610268277.1A CN105903467B (en) | 2016-04-27 | 2016-04-27 | The preparation method of Pd-only automobile exhaust catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610268277.1A CN105903467B (en) | 2016-04-27 | 2016-04-27 | The preparation method of Pd-only automobile exhaust catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105903467A true CN105903467A (en) | 2016-08-31 |
| CN105903467B CN105903467B (en) | 2018-03-16 |
Family
ID=56752118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610268277.1A Active CN105903467B (en) | 2016-04-27 | 2016-04-27 | The preparation method of Pd-only automobile exhaust catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105903467B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107519857A (en) * | 2017-08-16 | 2017-12-29 | 柳州申通汽车科技有限公司 | The processing technology of ternary catalyst for automobile tail gas |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003023A (en) * | 2006-01-19 | 2007-07-25 | 清华大学 | Method for preparing catalyst to purify automobile tail gas |
| WO2011092521A1 (en) * | 2010-02-01 | 2011-08-04 | Johnson Matthey Plc | Extruded scr filter |
| US20130004391A1 (en) * | 2010-04-14 | 2013-01-03 | Umicore Ag & Co. Kg | Reduction-catalyst-coated diesel particle filter having improved characteristics |
| CN104190438A (en) * | 2014-08-12 | 2014-12-10 | 淄博加华新材料资源有限公司 | High-performance cerium zirconium oxide and production method of high-performance cerium zirconium oxide |
| CN104772162A (en) * | 2015-04-11 | 2015-07-15 | 桂林理工大学 | Zr-Ce-Mn-Fe/ZSM-5 composite oxide catalyst for NOx reduction by using low-temperature NH3 and preparation method thereof |
-
2016
- 2016-04-27 CN CN201610268277.1A patent/CN105903467B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003023A (en) * | 2006-01-19 | 2007-07-25 | 清华大学 | Method for preparing catalyst to purify automobile tail gas |
| WO2011092521A1 (en) * | 2010-02-01 | 2011-08-04 | Johnson Matthey Plc | Extruded scr filter |
| US20130004391A1 (en) * | 2010-04-14 | 2013-01-03 | Umicore Ag & Co. Kg | Reduction-catalyst-coated diesel particle filter having improved characteristics |
| CN104190438A (en) * | 2014-08-12 | 2014-12-10 | 淄博加华新材料资源有限公司 | High-performance cerium zirconium oxide and production method of high-performance cerium zirconium oxide |
| CN104772162A (en) * | 2015-04-11 | 2015-07-15 | 桂林理工大学 | Zr-Ce-Mn-Fe/ZSM-5 composite oxide catalyst for NOx reduction by using low-temperature NH3 and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107519857A (en) * | 2017-08-16 | 2017-12-29 | 柳州申通汽车科技有限公司 | The processing technology of ternary catalyst for automobile tail gas |
| CN107519857B (en) * | 2017-08-16 | 2020-07-14 | 柳州申通汽车科技有限公司 | Processing technology of automobile exhaust three-way catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105903467B (en) | 2018-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105688905A (en) | Preparation technology of automobile exhaust catalyst | |
| CN109305924B (en) | Synthetic method of aminoanisole compound | |
| CN107029805B (en) | Carried noble metal nano-cluster catalytic composite materials and preparation method thereof | |
| RU2730496C2 (en) | Rhodium-containing catalysts for treating automotive exhausts | |
| CN102872865A (en) | Method for preparing honeycomb ceramic catalyst | |
| CN104148065A (en) | Catalyst used for methanation of carbon dioxide, preparation method therefor and applications thereof | |
| JP2012096234A (en) | Carrier carrying metal-containing colloidal particle and method of producing the same | |
| CN105597750B (en) | A kind of flawless three-way catalyst coating paste, catalyst and preparation method thereof | |
| CN111921526A (en) | Preparation method of single-coating three-way catalyst for gasoline vehicle | |
| CN106925266A (en) | Single coating three-way catalyst | |
| CN105797744A (en) | Preparation process of automobile tail gas ternary catalyst | |
| CN101890368A (en) | Method for preparing carbon-supported high-activity gold or gold-platinum alloy or gold-core platinum-shell structural nano catalyst | |
| CN105903467A (en) | Preparation method of palladium-only automobile exhaust catalyst | |
| CN105688933A (en) | Technology for preparing three-way catalyst with ball milling method | |
| CN105772025A (en) | Preparation method of automobile exhaust ternary catalyst | |
| CN105797708A (en) | Preparation method of ternary tail gas catalyst | |
| WO2006095392A1 (en) | Process for producing catalyst for discharge gas treatment | |
| JP2008173592A (en) | Composite material, composite material base material, composite material dispersion liquid, and production method used for the same | |
| CN110721683A (en) | Catalyst for liquid nitrogen tail gas washing oxidation under oxygen critical condition and preparation method and application thereof | |
| CN105772026A (en) | Preparation method of automobile exhaust catalyst | |
| EP2870997B1 (en) | Catalyst for emission gas purification and production method thereof | |
| CN105797737A (en) | Preparation method of ternary catalyst | |
| CN114425333B (en) | Catalyst for methane catalytic combustion and preparation method thereof | |
| CN109675557B (en) | Noble metal catalyst with high thermal stability and preparation method thereof | |
| CN104399488A (en) | Precious metal modified catalyst used for synthesizing ethanol, and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |